Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/125—Water, e.g. hydrated salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
  • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
  • B29C48/83—Heating or cooling the cylinders
  • B29C48/832—Heating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
  • C08J2201/03—Extrusion of the foamable blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2325/02—Homopolymers or copolymers of hydrocarbons
  • C08J2325/04—Homopolymers or copolymers of styrene
  • C08J2325/06—Polystyrene

Definitions

• the present invention relates to an extruded thermoplastic synthetic resin foam and a method for producing the same. More specifically, the present invention relates to a plate-shaped extruded thermoplastic synthetic resin foam having high heat insulation performance and appropriate strength properties, and particularly useful as a heat insulating material, and a method for producing the same.
• synthetic resin extruded foam Since synthetic resin extruded foam has excellent heat insulation performance, it is used as a building material for homes and other heat insulating materials, contributing to energy savings, and is one of the leading products in global warming prevention measures. It is expected as one.
• a production method using an evaporating foaming agent is mainly used.
• the evaporative foaming agent used here not only provides foaming energy but also exhibits a plasticizing function in the extrusion system.
• the evaporating foaming agent has a function of adjusting the bubble size and controlling the growth rate of the bubbles. In particular, it has a significant effect on the thermal conductivity that governs thermal insulation. Therefore, selection of such an evaporative foaming agent has always been a major research issue when developing extrusion foaming technology.
• foaming agents used in extruded synthetic resin foams include poorly permeable foaming agents that control the performance of foam after foaming, plasticization in an extruder, control of foaming energy and growth rate of air bubbles, etc.
• foaming agents used in extruded synthetic resin foams include poorly permeable foaming agents that control the performance of foam after foaming, plasticization in an extruder, control of foaming energy and growth rate of air bubbles, etc.
• a combination with an easily permeable foaming agent that affects the properties is used.
• fluorinated hydrocarbons such as 1-difluoro-1-chlorobenzene (hereinafter abbreviated as HCFC144b) as an example of chlorinated fluorinated hydrocarbon (HCFC)
• hydrocarbons include 1,1,1,2-tetratetrafluoroethane (hereinafter abbreviated as HFC134a), and examples of hydrocarbons include propane and butane.
• the group of easily permeable blowing agents includes, for example, methyl chloride and ethyl chloride, which are examples of halogenated hydrocarbons.
• HFCFC142b which is CFC
• methyl chloride is used as an example of the easily permeable foaming agent. It mainly consists of air bubbles with a diameter of 0.25 mm or less and air bubbles with a diameter of 0.4 to 1 mm.
• inorganic powder or water-absorbing polymer having many hydroxyl groups on its surface Water is used with the substance.
• WO 9 Z 5 439 90 discloses a gate acid powder in which magnesium gayate is a representative example as a water-absorbing medium.
• This section describes the contents to be used in conjunction with the use of water when obtaining a bubble (cell) structure in which two types of bubbles (large and small cells) coexist under the use of limited gas types and gas ratios. ing.
• This international publication As described above, the report shows the content under the limited conditions of limited gas types and gas ratios, and the technology has not been completed under a wide range of conditions. Further, when a large amount of magnesium silicate exemplified in the publication is added, it tends to be difficult to maintain closed cells. In addition, there is a tendency that inconvenience such as easy foaming failure due to extreme miniaturization of cells occurs. For this reason, there is a problem that the amount of magnesium silicate must be restricted and the amount of water to be added is limited due to the dispersibility in the extrusion system. I was
• Japanese Patent Application Laid-Open No. Hei 8-5202886 describes a method for producing extruded styrene-based resin foams using water as a part of the foaming agent, such as low-molecular-weight polymers, oligomers, and hydrophilic polymers.
• a method in which a styrene resin material has water solubility by means of mixing is disclosed.
• a limited amount of water is used as a part of the foaming agent. I have not been able to propose a body.
• the present invention has been made in view of the above prior art, and reduces or uses a foaming agent such as HCFC142b or methyl chloride, which has an effect on the environment such as ozone layer depletion and global warming.
• the object is to provide a foam having excellent heat insulation performance by using environmentally friendly water as a foaming agent without using it.
• the present inventors (1) have made intensive studies on how to disperse and disperse incompatible water in a thermoplastic synthetic resin uniformly and use it as a foaming agent. Among them, we focused on hydrous silicate minerals that possess a characteristic crystal structure and are effective in retaining water. Among them, even if a large amount is added, closed cells can be secured, and it has a characteristic that it has an appropriate nucleation action that does not cause molding defects due to extreme cell miniaturization. A hydrous gate mineral which can be increased, that is, bentonite, was found. Can heat bentonite When blended with plastic synthetic resin, the amount of water that can be uniformly dispersed and maintained in the molten thermoplastic synthetic resin can be increased, and the expansion ratio can be improved.
• thermoplastic synthetic resin extruded foam characterized in that bentonite is contained in an amount of 0.2 to 10 parts by weight based on 100 parts by weight of the thermoplastic synthetic resin.
• the air bubbles forming the extruded thermoplastic synthetic resin foam are mainly composed of air bubbles having a cell diameter of 0.25 mm or less and air bubbles having a cell diameter of 0.3 to lmm, and these air bubbles pass through the cell membrane. Any of the above (1) to (3), characterized in that bubbles having a cell diameter of 0.25 mm or less are dispersed in a sea-island shape and have an occupied area ratio of 10 to 90% per sectional area of the foam.
• thermoplastic synthetic resin foam according to any one of (1) to (5) above, wherein the thermoplastic synthetic resin is a polystyrene resin.
• thermoplastic synthetic resin foam according to any one of (1) to (6), wherein the foam is a plate having a thickness of 10 to 150 mm.
• thermoplastic synthetic resin foam according to any one of (1) to (7) above, wherein 0.05 to 3 parts by weight of liquid paraffin is used as a viscosity modifier.
• thermoplastic synthetic resin (9) A method for producing a foam in which a foaming agent is press-fitted into a heated and melted thermoplastic synthetic resin and extruded and foamed, wherein bentonite is added to the thermoplastic synthetic resin in an amount of 0.2 to 1 part by weight based on 100 parts by weight. 0 parts by weight, and using water as a foaming agent
• thermoplastic synthetic resin extruded foam (1) The method for producing a thermoplastic synthetic resin extruded foam according to any one of (8) to (8).
• the bentonite referred to in the present invention is a basic clay mineral whose main component is montmorillonite and contains associated minerals such as quartz, ⁇ -cristobalite, opal, feldspar, and mica.
• bentonite is mainly composed of silicon oxide, followed by aluminum oxide.
• montmorillonite consists of a thin silicate layer with a thickness of about 1 nm, the surface of the plate-like crystal particles is negatively charged, and exchangeable cations such as sodium and calcium are interposed between the layers. It is said to be a clay mineral that keeps charge neutrality, hydrates water molecules into exchangeable cations between layers when it comes into contact with water, and swells between layers.
• the magnesium silicate described in the above-mentioned publicly known gazette refers to a substance having silicon oxide as a main component and magnesium oxide being the next largest chemical component.
• bentonite used in the present invention include natural bentonite and purified bentonite.
• montmorillonite modified products such as organic bentonite, anion-based polymer-modified montmorillonite, silane-treated montmorillonite, and highly polar organic solvent composite montmorillonite are also included in the category.
• Bentonite can be obtained, for example, from Toyoko Mining Co., Ltd. as Bentonite Hotaka, Wenger, etc. Such bentonite can be used alone or in combination of two or more.
• the bentonite used here absorbs water that is not compatible with the thermoplastic synthetic resin. It is used because it is thought that a gel will be formed and it will be dispersed uniformly in the thermoplastic synthetic resin in the gel state.
• the blending amount of bentonite is preferably adjusted so as to be 0.2 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the synthetic resin. If the amount is less than 0.2 parts by weight, the amount of bentonite adsorbed by water is insufficient with respect to the amount of water injected, and pores are generated in the extruder due to non-dispersion of water, which tends to result in a molded article failure. .
• the mixing ratio of water / bentonite is in the range of 0.02 to 20 and preferably 0.25 to 2 by weight.
• thermoplastic synthetic resin extruded foam of the present invention is added with 0.2 to 10 parts by weight of bentonite based on 100 parts by weight of the thermoplastic synthetic resin, and then heated and melted and kneaded, and then 0.2 to 4 parts by weight of water (preferably). Is 0.3 to 3.5 parts by weight) or 0.2 to 4 parts by weight of water and a foaming agent other than water are press-fitted and then extruded and foamed in a low pressure region.
• a foam having such a large and small cell structure is excellent in heat insulation performance and mechanical strength.
• the excellent heat insulation performance of the foam having the large and small cell structure is that the heat flow moving through the uniform cell structure in the conventional foam having the uniform cell structure is the same as that of the present foam. This is presumed to be due to fragmentation by small bubbles having a diameter of 0.25 mm or less existing around large bubbles of 3 to 1 mm.
• the stress applied to the cell membrane is dispersed by, for example, fine bubbles having a bubble diameter of 0.25 mm or less, which are present in a sea-island shape, so that favorable bending characteristics are improved. It is presumed to be expressed.
• small cells having a cell diameter of 0.25 mm or less have an occupied area ratio of 10 to 90% per cross-sectional area of the foam.
• the occupied area ratio of the small cells is preferably 20 to 90%, more preferably 30 to 90%, and most preferably 40 to 90% per sectional area of the foam.
• the small bubble occupying area ratio is large because the heat insulating performance is improved.
• a conventional foam having a uniform cell structure or a foam having a large and small cell structure can be separately formed.
• a bentonite described above may be mixed with a water-absorbing polymer compound as a substance having an auxiliary effect, or an inorganic powder having a large number of hydroxyl groups on the surface.
• a water-absorbing polymer compound for example, it is available from Nippon Shokubai Co., Ltd. as a polyacrylate base resin such as Aqualic CA.
• the water-absorbing polymer acts in the same manner as bentonite. It is preferable to adjust the amount of the water-absorbing polymer compound to be 0.2 to 10 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the synthetic resin.
• the amount is less than the above range, the amount of water adsorbed by the water-absorbing polymer compound is insufficient with respect to the amount of water injected, and pores are generated in the extruder due to non-dispersion of water, resulting in a molded article failure. If the above range is exceeded, non-dispersion of the water-absorbing polymer compound occurs in the extruder, resulting in non-uniform air bubbles, resulting in deterioration and variation in the heat insulating performance of the foam. Since the gel of the water-absorbing polymer compound when absorbing water is much higher than that of bentonite, the gel tends to be non-dispersed in the extruder, so that it is preferably used in combination with bentonite.
• the inorganic powder having a large number of hydroxyl groups on its surface include, for example, anhydrous silica having a silanol group on its surface such as AEROSIL (average particle size: 12 ⁇ 10 ⁇ 3 m) of Nippon Aerosil Co., Ltd. Is raised.
• the compounding amount of the inorganic powder having a large number of hydroxyl groups on the surface is adjusted so as to be 0.05 to 2 parts by weight, preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the synthetic resin. Is preferably performed. If the amount is less than the above range, the number of generated fine bubbles tends to decrease, Also, when the above range is exceeded, fine bubbles tend to be hardly generated.
• the water used in the present invention is not particularly limited, and for example, pure water can be used.
• an evaporative foaming agent generally used in extrusion foaming is used as the foaming agent other than water used together with water in the present invention.
• foaming agents include ethers such as dimethyl ether, getyl ether, and methyl ethyl ether, methanol, ethanol, propyl alcohol, i-propyl alcohol, butyl alcohol, i-butyl alcohol, and t-butyl alcohol.
• Inorganic gas such as alcohol, carbon dioxide, nitrogen, argon, and helium exemplified by alcohol; saturated hydrocarbon having 3 to 6 carbon atoms such as propane, i-butane, n-butane, and pentane; methyl chloride; ethyl chloride; Halogenated hydrocarbons, 1-difluoro-1
• HCFC 142 b 1, 1, 1, 2-tetrafluroethane (HFC 134a), 1,1-difluoroethane (HFC 152a), 1, 1, 1-trifluorofluorene (HF C 143 a), 1,1,1,2,3,3-hexafluoropropane (HFC 236 ea), 1,1,1,3,3-Pentate fluoropropane (HFC 245 fa) And the like, and ketones such as acetone, dimethyl ketone and methyl ethyl ketone.
• These blowing agents can be used alone or in combination of two or more.
• mo 1 here is the sum of the number of mo 1 used water and the number of mo 1 of foaming agent other than water
• water or the blowing agent other than water and water may be added simultaneously by means of press-fitting after heating and melting, or may be separately press-fitted or added. It is not limited by the method of addition.
• the pressure when the water or the foaming agent other than water and water is injected into the heat-melt kneaded material is not particularly limited, and may be any pressure that can be injected at a pressure larger than the internal pressure of the extruder.
• the foamed product of the present invention can be obtained by adjusting the thermoplastic synthetic resin and the additives in predetermined amounts, kneading by heating, and extruding foam by press-fitting or adding water or a foaming agent other than water and water.
• the heating temperature, melt-kneading time and melt-kneading means when the thermoplastic synthetic resin and the additive are heated and melt-kneaded, and the heating temperature is not lower than the temperature at which the thermoplastic synthetic resin melts.
• the temperature may be 30 to 250 ° C, and the melt-kneading time cannot be determined unequivocally because it varies depending on the extrusion amount per unit time, the melt-kneading means, and the like.
• the time required for the additives to be uniformly dispersed can be selected, and the melt-kneading means may be, for example, a screw-type extruder, provided that it is used for normal extrusion foaming. There is no particular limitation.
• thermoplastic synthetic resin When the usage ratio of ordinary organic vaporizing blowing agents such as methyl chloride and HCFC142b as blowing agents other than water is small, the plasticizing effect of thermoplastic synthetic resin by these blowing agents in the extruder is reduced.
• the melt viscosity of the thermoplastic synthetic resin increases, and water and bentonite tend not to be uniformly dispersed.
• equipment abnormalities due to an increase in the load of the extruder and abnormal flow distribution of the thermoplastic synthetic resin in the foaming apparatus may occur. For example, as a countermeasure, adjust the viscosity of a plasticizer such as liquid paraffin. It is preferable to add an agent.
• Liquid paraffin is available from Mobil Oil Co., Ltd. as White Rex.
• the amount of the viscosity modifier is preferably adjusted to 0.05 to 3 parts by weight based on 100 parts by weight of the synthetic resin. If the amount is more than the above range, a dimensional change with respect to the temperature of the foam becomes severe, and a phenomenon that the heat resistant temperature is lowered occurs.
• thermoplastic synthetic resin used in the present invention for example, polystyrene resin, Thermoplastic resins such as polyethylene resin, polypropylene resin, and polyurethane resin can be mentioned.
• polystyrene resin, polyethylene resin, polypropylene resin, etc. can be suitably produced by extrusion foaming method. It is preferable to use a polystyrene-based resin which has excellent heat insulating properties and high rigidity, but is desired to be further improved in bending and the like.
• polystyrene resins include, for example, polystyrene, copolymers of styrene with methyl styrene, maleic anhydride, acrylic acid, acrylic acid ester, methacrylic acid-methacrylic acid ester, and polystyrene. And modified with appropriate addition of styrene * butadiene rubber (SBR).
• SBR styrene * butadiene rubber
• a nucleating agent may be added to the thermoplastic synthetic resin, if necessary.
• the nucleating agent include nucleating agents used in known extrusion foaming.
• Representative examples of such a nucleating agent include, for example, talc powder and calcium carbonate powder, and these nucleating agents can be used alone or in combination of two or more.
• the particle size of such a nucleating agent is preferably adjusted so as to be usually 3 to 100 °, preferably 5 to 20; m.
• the nucleating agent is mainly used for adjusting cells having a cell diameter of 0.3 to l mm in the obtained foam.
• the compounding amount of the nucleating agent is 100 parts by weight of the thermoplastic synthetic resin. It is preferable to adjust the amount to be 0.05 to 5 parts by weight, especially 0.1 to 2.5 parts by weight.
• the amount is less than the above range, the effect of adding the nucleating agent is not sufficiently exhibited, and the cell size tends to be enlarged. Although the cell size becomes small, it is difficult to achieve the target density.
• the water-absorbing polymer compound, the nucleating agent, the inorganic powder having a large number of hydroxyl groups on the surface for example, a flame retardant such as hexacyclopromododecane, a polymer-type hindered General antioxidants such as phenolic compounds, lubricants such as barium stearate and magnesium stearate, and colorants
• a flame retardant such as hexacyclopromododecane
• a polymer-type hindered General antioxidants such as phenolic compounds
• lubricants such as barium stearate and magnesium stearate
• colorants colorants
• a plate-like foam having a large cross-sectional area is formed by using a molding die and a molding roll in which the foam obtained by releasing the pressure from the slit die is placed in close contact with or in contact with the slit die.
• a general method of molding can be used.
• the cell diameter of the foam having a uniform cell structure is not particularly limited, but is adjusted to a cell diameter of 0.7 mm or less, preferably 0.3 mm or less in order to provide preferable heat insulating properties, mechanical strength, and workability. Things are preferred.
• the thickness of the foam of the present invention is not particularly limited.
• a material having a thickness like a normal plate-like material is more preferable than a thin material such as a sheet, and usually 10 to 150 mm, preferably It is 20 to 100 mm.
• the density of the foam of the present invention is preferably from 15 to 50 kgZm 3 , more preferably from 25 to 40 kgZms, in order to impart light weight and excellent heat insulating properties and flexural strength.
• thermoplastic synthetic resin foam of the present invention and a method for producing the same will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.
• physical properties of the obtained foam a foam density, a foam appearance, a foam thermal conductivity, and an air bubble occupying area ratio were examined according to the following methods.
• Foam density foam weight Z foam volume
• the foam was visually observed, and the case where the epidermis was smooth and there were no giant bubbles such as voids and non-uniform air bubbles was evaluated as “ ⁇ ”.
• the ratio of the area occupied by the cells having a cell diameter of 0.25 mm or less per cross-sectional area of the foam was determined as follows.
• the bubble having a bubble diameter of 0.25 mm or less is a bubble having a circle equivalent diameter of 0.25 mm or less.
• the primary processing image is taken into an image processing device (Pierce Co., Ltd., product number: PIAS-II), and the dark and light colors are identified, that is, whether or not they are painted with black ink. . d) Of the dark colored part, the part corresponding to the area of a circle with a diameter of 7.5 mm or less, that is, the diameter in the thickness direction is long, but the area is only the area of a circle with a diameter of 7.5 mm or less. Lighten the parts that do not work and correct the dark parts.
• Polystyrene resin (manufactured by Kanegafuchi Chemical Industry Co., Ltd., trade name: Canelite PS, Melt Index (Ml): 3) 2 parts by weight of bentonite (manufactured by Toyshun Mining Co., Ltd., Wengel 15) per 100 parts by weight Parts, anhydrous silica (AEROS IL, manufactured by Nippon Aerosil Co., Ltd.) as an inorganic powder having a large number of hydroxyl groups 0.1 part by weight, talc 0.3 parts by weight as a nucleating agent, hexyl mouth mocyclododecane 3 as a flame retardant Add 0.3 parts by weight of barium stearate as a lubricant and knead by heating to 200 ° C in an extruder.
• bentonite manufactured by Toyshun Mining Co., Ltd., Wengel 15
• anhydrous silica AEROS IL, manufactured by Nippon Aero
• a foam was obtained in the same manner as in Example 1 except that the injection amount of water was 1.5 parts by weight, and the injection amount of the evaporative foaming agent was changed to 1.5 parts by weight of methyl chloride and 3 parts by weight of propane. Was. The results are shown in Table 1. Foam density even when methyl chloride is further reduced
• a foam having good appearance was obtained while maintaining a high expansion ratio of 30 kg Zm 3 .
• Example 1 No bentonite was added, no water was injected, 5.5 parts by weight of evaporative foaming agent, methyl chloride and 3 parts by weight of propane were injected, and the other conditions were the same as in Example 1. I got a body. The results are shown in Table 1. A foam having a foam density of 30 kg Zm 3 and good appearance was obtained. However, the amount of methyl chloride used is large.
• Example 3 1.5 parts by weight of bentonite, 0.5 parts by weight of water injected, 2.7 parts by weight of evaporative foaming agent, methyl chloride, and 1 part by weight of HCFC 142b A foam was obtained under the same conditions as in Example 1. The results are shown in Table 1. Compared with Comparative Example 4 below, even with a reduced amount of methyl chloride, a foam having a good appearance was obtained while maintaining a high foaming ratio of a foam density of 29 kg / m.
• Example 2 1.5 parts by weight of bentonite, 1.5 parts by weight of water were injected, and 1 part by weight of HCFC 142b, an evaporative foaming agent, was injected under the same conditions as in Example 1. A foam was obtained. The results are shown in Table 1. And without the use of methyl chloride also while maintaining a high expansion ratio of the foam density 29 k gZm 3, good appearance foam was obtained.
• Examples 8 to 13 below are examples relating to a foam having a cell structure composed of large and small cells, and Comparative Examples 5 to 9 are comparative examples thereof.
• Polystyrene resin manufactured by A & M Styrene Co., Ltd., trade name: Sugalon G9401, Melt Index (MI): 2.0
• Bentonite manufactured by Toyshun Mining Co., Ltd.
• Bentonite Hotaka 0.1 part by weight of talc as a nucleating agent, 3 parts by weight of moclododecane hexab mouth as a flame retardant, and 0.3 parts by weight of barium stearate as a lubricant.
• a foam having a good appearance with a foam density of 3 lkgZm 3 , a small cell occupying area ratio of 33%, and a foam thermal conductivity of 0.028 WZmK was obtained. Compared with Comparative Example 5 below, the small bubble occupation area ratio is increased, and the thermal conductivity of the foam is improved.
• a foam was obtained in the same manner as in Example 8, except that the amount of water injected was changed to 1 part by weight. The results are shown in Table 2.
• a foam having a good appearance with a foam density of 31 kg / m 3 , a small cell occupying area ratio of 51%, and a foam thermal conductivity of 0.027 WZmK was obtained. Compared to Comparative Example 6 below, the small bubble occupation area ratio was increased, and the thermal conductivity of the foam was improved.
• a foam was obtained in the same manner as in Example 8, except that the amount of water injected was changed to 2 parts by weight. The results are shown in Table 2. A foam having a good appearance with a foam density of 31 kg / m 3 , a small cell occupying area ratio of 54%, and a foam thermal conductivity of 0.027 WZmK was obtained.
• Example 1 1 The amount of water injected was 1 part by weight, and 3 parts by weight of methyl chloride and 9 parts by weight of HCFC142b, which are evaporating foaming agents, were pressed in, and the other conditions were the same as in Example 8 to obtain a foam.
• the results are shown in Table 2.
• a foam having a good appearance with a foam density of 30 kgZm 3 , a small cell occupying area ratio of 47%, and a foam thermal conductivity of 0.026 WZmK was obtained. Compared to Comparative Example 7 below, the small bubble occupation area ratio was increased, and the foam thermal conductivity was improved.
• the injection amount of water was 2 parts by weight, and 3 parts by weight of methyl chloride and 9 parts by weight of HCFC142b, which are evaporative foaming agents, were injected under the same conditions as in Example 8 to obtain a foam.
• the results are shown in Table 2.
• a foam having a good appearance with a foam density of 30 kgZm 3 , a small cell occupying area ratio of 52%, and a foam thermal conductivity of 0.026 W / mK was obtained. Compared with Comparative Examples 8 to 10 below, the small bubble occupying area ratio is increased, and the thermal conductivity of the foam is improved.
• the amount of water injected was 1.8 parts by weight, and 9 parts by weight of HCFC 142b, which is an evaporating foaming agent, was injected under the same conditions as in Example 8 to obtain a foam.
• the results are shown in Table 2.
• Bentonite was changed to anhydrous silica (AEROS IL, manufactured by Nippon Aerosil Co., Ltd.), 1 part by weight, water injection was 2 parts by weight, evaporative blowing agent, methyl chloride 3 parts by weight, HCFC 142 b 9 parts by weight were press-fitted, and the other conditions were the same as in Example 8 to obtain a foam.
• the results are shown in Table 2. Only a foam having poor appearance, which is considered to be due to poor water dispersion, was obtained. The foam had a foam density of 35 kg / m 3 , a small cell occupying area ratio of 15%, and a foam thermal conductivity of 0.031 W / mK. Comparative Example 10
• Bentonite was changed to magnesium gayate (Rabonite, manufactured by Nippon Silica Co., Ltd.), 1 part by weight, water injection was 2 parts by weight, evaporative blowing agent, 3 parts by weight of methyl chloride, HCFC 142 b 9 parts by weight were press-fitted, and the other conditions were the same as in Example 8 to obtain a foam.
• the results are shown in Table 2. Poor foam formation due to cell miniaturization occurred, and only a foam with an unsmooth skin and poor appearance was obtained.
• the foam had a foam density of 34 kg Zm 3 , a small cell occupying area ratio of 18%, and a foam thermal conductivity of 0.030 WZm K.
• Methyl chloride (parts by weight) 3 3 3 3 3 3 3 3
• Anhydrous silica (parts by weight) 1 Magnesium gayate (parts by weight) 1 Foam density (kgZm 3 ) 31 31 31 30 30 42 31 35 33 34 35 34 Appearance of foam ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ XX XXXX Small bubble occupation area ratio (%) 33 51 54 47 52 48 13 1 1 17 18 15 18 Foam thermal conductivity (WZmK) 0.028 0.027 0.027 0.026 0.026 0.026 0.029 0.031 0.030 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030 0.031 0.030
• ADVANTAGE OF THE INVENTION even if the water which is excellent in environmental compatibility is used effectively as a foaming agent, even if the foaming agent which affects an environment is reduced, the lightweight foam which had the outstanding heat insulation performance can be obtained. Further, in a foam in which large and small bubbles are mixed, the formation of small bubbles is good, and the occupied area ratio of the small bubbles is improved. In this way, a more desirable mixed structure of large and small bubbles can be obtained, so that the heat insulation performance can be further improved.

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